Silicone Resins And Their Use in Polymers

Abstract

The invention relates to silicone resins comprising metallosiloxane which contains Si—O-Metal bonds or borosiloxane containing Si—O—B bonds and potentially Si—O—Si and/or B—O—B bonds. It also relates to the preparation of such silicone resins and to their use in thermoplastic or thermosetting organic polymer or rubber or thermoplastic/rubber blends compositions to reduce the flammability or enhanced scratch and/or abrasion resistance of the organic polymer compositions. It further relates to coatings made of such silicone resins for scratch resistance enhancement or flame retardant properties.

1 . A silicone resin comprising:
 a. at least one metallosiloxane comprising Si—O-M bonds, wherein Metal M is chosen from Transition Group metals, IIIA Group elements, Zr and Sn; and   b. at least one organic group comprising phosphorus and/or nitrogen with the proviso that when the Metal M is Al, the organic group is different than —(CH 2 ) 3 NH 2 ,   c. wherein, when present, phosphorous is linked to Si through carbon atom(s).   
     
     
         2 . The silicone resin according to  claim 1  which contains T units; D units; M″ units and/or Q units. 
     
     
         3 . The silicone resin according to  claim 1  wherein the Metal M is boron, aluminum, titanium, tin or any mixture thereof. 
     
     
         4 . The silicone resin according to  claim 1 , comprising at least one organic group containing phosphorus. 
     
     
         5 . The silicone resin according to  claim 4  wherein the resin contains at least one phosphine and/or phosphine oxide and/or phosphinate and/or phosphinite and/or phosphonite and/or phosphate and/or phosphonate, and/or a phosphate moiety present in a M unit of the formula RPR2SiO1/2 and/or a D unit of the formula RPRSiO2/2 and/or a T unit of the formula RPSiO3/2, where RP is an alkyl, cycloalkyl, alkenyl, alkynyl or aryl group having 1 to 20 carbon atoms containing a phosphine and/or phosphine oxide and/or phosphinate and/or phosphinite and/or phosphonite and/or phosphate and/or phosphonate, and/or a phosphate substituent, and each group R is independently an alkyl, cycloalkyl, alkenyl, alkynyl or aryl group having 1 to 20 carbon atoms. 
     
     
         6 . The silicone resin according to  claim 5 , wherein the phosphine and/or phosphine oxide and/or phosphinate and/or phosphinite and/or phosphonite and/or phosphate and/or phosphonate, and/or the phosphate moiety is present in a T unit of the formula RPSiO3/2. 
     
     
         7 . The silicone resin according to  claim 4 , wherein the group RP has the formula 
       
         
           
           
               
               
           
         
       
       where A is a divalent hydrocarbon group having 1 to 20 carbon atoms, where R* is an hydrogen, alkyl or aryl group having 1 to 12 carbon atoms, and Z is a group of the formula —OR* or an alkyl, cycloalkyl, alkenyl, alkynyl or aryl group having 1 to 20 carbon atoms, and when 2 —OR* are present, R* can be the same or different. 
     
     
         8 . The silicone resin according to  claim 4 , wherein the group RP has the formula 
       
         
           
           
               
               
           
         
       
       where A is a divalent hydrocarbon group having 1 to 20 carbon atoms. 
     
     
         9 . The silicone resin according to  claim 1  wherein the molar ratio of Metal atom to Si atom ranges from 0.01 to 2. 
     
     
         10 . Method for the preparation of a silicone resin according to  claim 1 , wherein:
 a. A Metal containing material optionally free of chlorine atoms;   b. A phosphorylated or nitrogenated alkoxysilane or hydroxysilane or alkoxysiloxane or hydroxysiloxane; and   c. Optionally an alkoxysilane or hydroxysilane or alkoxysiloxane or hydroxysiloxane;   
       are hydrolysed and condensed to form metallosiloxane Si—O-M bonds optionally in the presence of an inorganic filler. 
     
     
         11 . Method according to  claim 10  wherein the a. Metal containing material is at least one boron containing material selected from (i) boric acid of the formula B(OH)3, any of its salts or boric anhydride, (ii) boronic acid of the formula R1B(OH)2, (iii) alkoxyborate of formulae B(OR2)3 or R1B(OR2)2, a mixture containing at least two or more of a.(i), a.(ii) or a.(iii), where R1 and R2 are independently alkyl, alkenyl, aryl or arylalkyl substituents. 
     
     
         12 . Method according to  claim 10  wherein the a. Metal containing material has general formula M(R3)m where m=1 to 7 depending on the oxidation state of the Metal, and wherein the a. Metal containing material is selected from
 i alkoxymetals where R3=OR′ and R′ is an alkyl group, and 
 ii metal hydroxyl where R3=OH. 
 
     
     
         13 . (canceled) 
     
     
         14 . (canceled) 
     
     
         15 . A thermoplastic or thermoset organic polymer or rubbers or thermoplastic/rubbers blends composition comprising a thermoplastic or thermoset organic polymer or rubbers or thermoplastic/rubbers blends and a silicone resin as claimed in  claim 1 . 
     
     
         16 . A thermoplastic or thermoset organic polymer composition according to  claim 15  further comprising a flame retardant additive, wherein the flame retardant additive is selected from metal hydrates, zinc borates, phosphorus and/or nitrogen containing additives, carbon based additives, nanoclays, red phosphorous, silica, aluminosilicates, magnesium silicate (talc), silicone gum, sulfur based additives, or polyols. 
     
     
         17 . A fire- or scratch and/or abrasion resistant coating on a substrate wherein the coating comprises a silicone resin according to  claim 1 . 
     
     
         18 . (canceled) 
     
     
         19 . A thermoplastic or thermoset organic polymer composition according to  claim 16 , wherein the flame retardant additive is selected from magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, boron phosphate, expandable graphite, carbon nanotubes, sulfonate, ammonium sulfamate, potassium diphenyl sulfone sulfonate (KSS), thiourea derivatives, pentaerythritol, dipentaerythritol, tripentaerythritol or polyvinylalcohol.